The Constituents of Marine Sponges. VI. Diterpenoid Metabolites of the New Zealand Sponge Chelonaplysilla violacea

Bergquist, P. L.; Bowden, Bruce F.; Cambie, R. C.; Craw, P. A.; Karuso, Peter; Poiner, Anthony; Taylor, WC

doi:10.1071/ch9930623

Cited by 37 publications

(49 citation statements)

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“…[2] As shown in Figure 1, there are several natural products that share some of norrisolide's structural features. [6] Chromodorolides A [7] and B [8] can be found in the same aplysillid sponge as the cheviolenes. Likewise, chelonoplysin, norrlandin, and cheviolenes C and E have norrisolide's hydrophobic hydrindane ring system.…”

Section: Introductionmentioning

confidence: 99%

Concise Synthesis of Norrisolide

Granger

Snapper

2012

Eur J Org Chem

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The marine natural product norrisolide has been synthesized in a convergent manner with a longest linear sequence of 14 steps. The hydrindane portion of the molecules is prepared through conjugate addition of a functionalized allyl group into cyclopentenone, followed by stereoselective trapping of the enolate generated from the resulting enol silyl ether with an allyl electrophile. Ring‐closing metathesis then establishes the 6–5 ring system. Likewise, selective preparation of the side chain features an enantioselective cyclopropanation of furan‐2‐one, followed by rearrangement and hydrogenation. Coupling of the two major fragments through a Shapiro reaction, followed by reduction and olefination then completes the carbon framework of the natural product. The final steps of the synthesis involve adjustments to the oxidation state of the side chain. New strategies to generate both the hydrindane core and the oxidized side chain has allowed for the more concise and efficient preparation of the natural product.

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Section: Introductionmentioning

confidence: 99%

Concise Synthesis of Norrisolide

Granger

Snapper

2012

Eur J Org Chem

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“…2). For example, aplyroseol-1 (4, R 1 = H, R 2 = Me, R 3 = OAc), was isolated from the dendroceratid sponges Aplysilla rosea [12,13], Dendrilla rosea [14] Aplysilla polyrhapis [15], and Chelonaplysilla violacea [16] and also from the nudibranches Chromodoris obsoleta [17] and Chromodoris inopinata [18]. Anti-tumor activity against the P388 mouse leukaemia cell line in vivo showed no significant activity.…”

Section: Intact Spongiane Skeletonmentioning

confidence: 99%

“…Aplyroseol-14 (4, R 1 = R 3 = H, R 2 = CH 2 OAc) and aplyroseol-16 (4, R 1 = OH, R 2 = CH 2 OAc, R 3 = OAc) have been isolated more recently also from the sponge Aplysilla rosea [24], whereas the cytotoxic γ-lactone spongian-16-one (4, R 1 = H, R 2 = Me, R 3 = H) has been found in several species such as Dictyodendrilla cavernosa [22], Chelonaplysilla violacea [16,23], Aplysilla var. sulphurea [24], and also in the mollusks Chromodoris obsoleta [17], C. petechialis [25], and C. inopinata [18].…”

Section: Intact Spongiane Skeletonmentioning

confidence: 99%

Author Index To Volume 2

2007

CBC

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In this review we cover the structures, occurrence, biological activities and synthesis of all the spongianes and rearranged spongianes since their discovery in 1974. We have given special attention to structure revisions and biological properties of these polycyclic terpenoids of exclusive marine origin. However, an important part of the review describes the synthetic efforts in the field. Thus, this part has been subdivided into syntheses from other natural products, syntheses by biomimetic approaches and other approaches including enantioselective total syntheses. Marine terpenoids are typical constituents of the secondary metabolite composition of marine flora and fauna. These isoprenoid-derived compounds are common in almost all marine phyla and show a wide range of novel structures. Although most of them are also present in terrestrial organisms, the occurrence of a few skeletons is restricted to certain marine species. In this review we focus our attention to diterpenoids characterized by polycyclic structures having either the spongiane (I, C 20 ) (Fig. 1) carbon framework or several degraded or rearranged spongiane-derived skeletons.Spongiane diterpenoids are bioactive natural products isolated exclusively from sponges and marine shell-less mollusks (nudibranchs), which are believed to be able of sequestering the spongian-derived metabolites from the sponges, soft corals, hydroids and other sessile marine invertebrates on which they feed. Most of these compounds play a key role as eco-physiological mediators and are of interest for potential applications as therapeutic agents.Spongianes having the characteristic carbon skeleton I (Fig. 1) have been reviewed up to 1990 and listed in the Dictionary of terpenoids [1]. During the last two decades, many new members of this family of natural products have been isolated and described in specific reviews on naturally occurring diterpenoids by Professor Hanson [2], and the excellent reviewing work on marine natural products by Professor Faulkner [3,4], now continued by the team of Professor Blunt [5,6], all of which have mainly covered the isolation and structural aspects of spongianes. A recent review on the chemistry of diterpenes isolated from marine opisthobranchs, has also included articles on isolation and structure determination of spongianes up to 1999 [7]. The latter also covered some synthetic studies of this class of substances. To the best of our knowledge, there is only one more report dealing with the initial studies towards the synthesis of spongianes [8]. We now provide full coverage of recent advances in the field including a comprehensive description of the synthetic approaches and syntheses reported in the literature on spongianes up to march 2006. STRUCTURE, OCCURRENCE AND BIOLOGICAL ACTIVITYThe semisystematic naming of this family of diterpenoids was introduced in 1979 following the isolation of the first members of

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“…These diterpenoids can be further subdivided into two families that differ by the orientation of the hydrocarbon fragment. In the largest collection, the hydrocarbon moiety resides on the more sterically hindered concave face of the cis-dioxabicyclo-[3.3.0]octan-3-one fragment, exemplified by macfarlandin C (2), [2] whereas cheloviolene A (3) [3] is representative of members in which the hydrocarbon unit resides on the convex face.…”

mentioning

confidence: 99%

Enantioselective Total Synthesis of Macfarlandin C, a Spongian Diterpenoid Harboring a Concave‐Substituted cis‐Dioxabicyclo[3.3.0]octanone Fragment

et al. 2020

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The enantioselective total synthesis of the rearranged spongian diterpenoid (−)‐macfarlandin C is reported. This is the first synthesis of a rearranged spongian diterpenoid in which the bulky hydrocarbon fragment is joined via a quaternary carbon to the highly hindered concave face of the cis‐2,8‐dioxabicyclo[3.3.0]octan‐3‐one moiety. The strategy involves a late‐stage fragment coupling between a tertiary carbon radical and an electrophilic butenolide resulting in the stereoselective formation of vicinal quaternary and tertiary stereocenters. A stereoselective Mukaiyama hydration that orients a pendant carboxymethyl side chain cis to the bulky octahydronapthalene substituent was pivotal in fashioning the challenging concave‐substituted cis‐dioxabicyclo[3.3.0]octanone fragment.

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The Constituents of Marine Sponges. VI. Diterpenoid Metabolites of the New Zealand Sponge Chelonaplysilla violacea

Cited by 37 publications

References 0 publications

Concise Synthesis of Norrisolide

Concise Synthesis of Norrisolide

Author Index To Volume 2

Enantioselective Total Synthesis of Macfarlandin C, a Spongian Diterpenoid Harboring a Concave‐Substituted cis‐Dioxabicyclo[3.3.0]octanone Fragment

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